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Carbon 45 (2007) 30273035 www.elsevier.com/locate/carbon

Electrical properties of dierent types of carbon ber reinforced plastics (CFRPs) and hybrid CFRPs
C.Q. Yang
a

a,*

, Z.S. Wu

a,b

, H. Huang

International Institute for Urban System Engineering, Southeast University, Nanjing 210096, China b Department of Urban and Civil Engineering, Ibaraki University, Hitachi 316-8511, Japan Received 3 December 2006; accepted 1 September 2007 Available online 8 September 2007

Abstract The electrical resistance (ER)time, currentvoltage and ERtemperature behaviors of carbon ber reinforced plastics (CFRPs) reinforced with high strength (HS), medium modulus (MM), and high modulus (HM) carbon bers were studied. At the same time, the electrical properties of hybrid CFRPs (HCFRPs) reinforced with more than one type of carbon bers were also studied. It was shown that the value of the current inuences the electrical stability and the ER measurement accuracy. In order to obtain an accurate ER measurement, the current should be larger than 1.5 mA. All the CFRPs and HCFRPs are characterized by linear currentvoltage and Ohmic behaviors. A negative temperature coecient (NTC) behavior is exhibited for all types of specimens. The NTCs of the CFRPs reinforced with HS, MM and HM carbon bers are 0.038, 0.033 and 0.094, respectively. For the specimens of HCFRPs containing HM carbon bers, the NTC becomes larger with increasing the volume fraction of HM carbon bers. The good linear and reversible relationship between the change in ER and temperature indicates that the CFRPs and HCFRPs may be used as temperature sensors. 2007 Elsevier Ltd. All rights reserved.

1. Introduction In recent decades, carbon ber (CF) reinforced plastics (CFRPs) have been widely investigated and applied to aerospace, civil engineering, auto industry and so on because of their superior mechanical properties (highstrength and high-stiness-weight ratios), low density, good environmental compatibility, long-term durability and high resistance to chemical corrosion, pressure and humidity. The reinforcing phases of the CFRP composites may be continuous carbon bers (CCFs), short carbon bers (SCFs) and carbon blacks (CBs). From the standpoint of mechanical properties, CCFs are more eective than SCFs and CBs as reinforcements. In addition to the excellent properties mentioned above, another important property of the CFRPs is their good
Corresponding author. Fax: +86 25 83793232. E-mail addresses: ycqjxx@hotmail.com, ycq@hcs.ibaraki.ac.jp (C.Q. Yang). 0008-6223/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2007.09.001
*

electrical conductivity and piezoresistivity. Generally, under tension, the resistivity increases linearly with applied strain/stress; under compression, it decreases linearly, as is called piezoresistivity. These electrical properties provide the CFRPs with some potential applications in strain/stress sensing, health monitoring, damage detecting, chemical and thermal sensing in terms of their electrical resistance (ER) variations with mechanical, chemical and thermal changes [113]. Thus, high value-added CFRPs can be obtained through fully using the electrical properties of carbon bers. The initiation and propagation of fatal fractures in the CFRPs and structures strengthened with CFRPs could be qualitatively identied through measuring the change in ER. These investigations revealed that the ER measurement method might be a promising method for improving the value-added of the CFRPs and as-strengthened structures. Unfortunately, the CFRPs are a very young group of material in comparison with the traditional metal, ceramic and other materials, which results in a shortage of knowl-

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C.Q. Yang et al. / Carbon 45 (2007) 30273035

edge about their long-term properties. Furthermore, the CFRPs with only one type of carbon bers as the reinforcing phase are inherently characterized by fragility, that is, the energy release of them is mainly elastic and sudden. Such a mechanical behavior often leads to sudden and fatal ruptures of the CFRPs and strengthened structures without any warnings. In order to overcome the inherent fragility, the hybridization with several types of bers as reinforcing phases had been proposed and investigated to obtain a pseudo-ductile behavior [8,1316]. Moreover, for the CFRPs with only one single type of carbon bers, the change in ER is very small before their nal failures. This greatly impairs the sensing performance of the CFRPs. The authors research group had carried out a series of investigations about the mechanical and electrical behaviors of hybrid CFRPs (HCFRPs) to upgrade their mechanical and electrical properties, and proposed their mechanical and sensing models based on the ER measurement method [69]. From these studies, it was shown that the inherent fragility of the CFRPs could be eectively avoided through a hybridization of some proper types of bers. Similarly, the electrical behavior was upgraded as well. For the CFRPs, the measurable change in ER was, generally, smaller than 2%; whereas for the HCFRPs, the measurable change in ER was improved up to several hundred percent. Since the gradual fractures of dierent types of carbon bers led to some denite sudden jumps in ER at dierent strains, the HCFRPs could provide a stage-based sensing for practical structures. The applications of the HCFRPs in the forms of sheet and rod to concrete structures were also studied to develop smart concrete structures with a self-structural health monitoring function, wherein the HCFRPs were used for both sensing and reinforcing purposes [6,9]. For a satisfactory self-sensing of the CFRPs, the basic electrical properties such as currentvoltage and ERtemperature behaviors were also studied. Keiji and Yoshihiro [17] investigated the electrical properties of the CFRPs reinforced with CCFs, and pointed out that the ER in 90 direction decreased with increasing the temperature while those in 0 and 45 directions were almost independent of temperature. The currentvoltage and inuence of temperature on the resistivity of the CFRPs lled with SCFs and CBs had been extensively investigated [1825]. According to the study of Chekanov et al. [18], the currentvoltage behavior of the CFRPs lled with SCFs was related to the volume content of SCFs. A non-Ohmic behavior was exhibited when the content of SCFs was less than 8%; an Ohmic behavior was exhibited when the content was more than 20%. His research also indicated that the resistivity of the CFRPs with SCFs showed a positive temperature coecient (PTC) behavior before the melting point of polymer matrix. He attributed the main reason for the PTC behavior to the separation of SCFs with heating. In his case, the relationship between resistivity and temperature was not reversible since not all electrical con-

tacts opened during heating were recovered during cooling, and the values of initial resistivity increased gradually as the heating cycles progressed. For the CFRPs lled with SCFs and CBs, the dependence of ER on temperature is relatively complicated. Generally, a PTC electrical behavior is presented before the melting point of polymer matrix, followed by a steep NTC behavior around the melting point. It was reported that the PTC behavior of the CFRPs lled with SCFs and CBs was due to the dierence in the thermal expansion coecients between the polymer matrix and SCFs (CBs) llers. The thermal expansion before the melting point of polymer matrix resulted in the breakup of the electrically conducting network with a consequent increase in resistivity [23]. The NTC behavior had been explained in terms of the formation of new networks of conductive elements and the reparation of disconnected conductive pathways [24,25]. In this paper, the electrical behaviors of dierent types of CFRPs and HCFRPs were studied in detail, especially the relationship between ER and temperature. The specimens were subjected to a cyclic heating and cooling test. It was shown that the current and temperature had some inuence on the electrical behavior of the CFRPs and HCFRPs. High currents are in favor of enhancing the ER measurement accuracy and electrical stability. A linear currentvoltage characteristic and an Ohmic behavior are demonstrated for all specimens. The ER decreases linearly with increasing the temperature. Moreover, the relationship between ER and temperature is experimentally conrmed to be stable and reversible under cyclic heating tests. A temperature sensing feasibility of the CFRPs and HCFRPs is thus demonstrated in this investigation.
2. Experimental 2.1. Materials
Specimens were fabricated with three types of pitch-based continuous carbon bers C1, C5 and C8 with a diameter of 7 lm, which were used as HS, MM and HM carbon bers, respectively. The mechanical properties of the carbon bers are listed in Table 1. FR-E3P standard epoxy resins and hardeners with a mix ratio by weight of 2:1 were used to impregnate the carbon bers, serving as plastic matrices. The tensile strength and elastic modulus of the epoxy resins are 52 MPa and 3.45 GPa. All the carbon bers used in this study are continuous carbon bers. Without special elucidation, the term of carbon bers means continuous carbon bers in the following sections. In a hybrid, each type of carbon bers has a dierent function. The function of dierent types of carbon bers in upgrading mechanical properties may be referred to [8]. Herein, the electrical function of each type of

Table 1 Properties of the carbon bers used in this study Type of tows C1 C5 C8 Tensile strength (GPa) 4.90 2.75 1.90 Youngs modulus (GPa) 230 392 640 Tex Density (g/cm3) 1.80 1.81 2.12 Filament

800 728 890

12,000 6,000 6,000

C.Q. Yang et al. / Carbon 45 (2007) 30273035 carbon bers is concisely addressed. Each type of carbon bers ruptures at a certain strain approximating to its nal strain, and the rupture leads to a sudden jump in ER. C8 as HM carbon bers ruptures at a low strain and provides a warning about the inchoate damage of the HCFRPs or strengthened structures. C5 is used as MM carbon bers to increase the number of jumps in ER with a nal object to enhance the measurable damage stage number. C1 is used as HS carbon bers to carry electrical conduction after the ruptures of HM and MM carbon bers and provides an important warning of the fatal ruptures of HCFRP-based structures. Before the rupture of carbon bers and between two jumps in ER, the ER increases with strain/stress linearly due to the piezoresistivity of carbon bers, which reveals that the HCFRPs can be used as strain sensor as well. The type and composition of carbon bers in the HCFRPs can be designed according to specic sensing requirements. Through a rational design, each jump in ER is adjusted to correspond to one certain damage stage, and thus a stage-based sensing of the HCFRPs for practical structures is realized. Indeed, the failure of practical structures can be divided into several stages. For example, the failure of infrastructures may be divided into concrete cracking, propagation of cracks, yielding and rupture of steel reinforcements and nal rupture. The HCFRPs with several types of carbon bers can meet the stage-based sensing requirement and provide some necessary warnings for practical structures.

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CFRPs reinforced with single type of carbon bers and four types were HCFRPs reinforced with multi-types of carbon bers. The compositions of the specimens are shown in Table 2. All the specimens were with a dimension of 200 mm in length and 5 mm in width. In this table, 1 means that the specimen consists of one lay of corresponding type of carbon bers. For example, specimen A consists of one layer of C1 and specimen F consists of one layer of each type of C1, C5 and C8 carbon bers.

2.3. Testing method

The ER was measured with a four-probe method. A small current of 5 mA generated by a DC generator was introduced into the specimens. The voltage of each specimen was measured with a 302Data Logger and a notebook with an accuracy of 0.001 mV. Then according to Ohms law, the ER was obtained. All the specimens were arranged in series, so the voltages of all specimens were measured with the data logger at the same time. The specimens were heated with a rubber resistive heater, and the temperature was controlled with a Pt100 temperature controller. When the temperature was incrementally increased every 2 C, it was held for 10 min for a thermal equilibrium throughout all the specimens. Then the voltages of all the specimens as well as temperature were synchronously measured with the 302Data Logger and thermocouples.

2.2. Fabrication of specimens

Firstly, the carbon bers were pretensioned for 5 h with a weight of 1 kg to make the carbon bers as straight as possible. The curve of carbon bers aects the sensing properties of CFRPs/HCFRPs especially when they are subjected to tension or compression [8]. Then, the carbon bers were impregnated with FR-E3P standard epoxy resins. During impregnation, it is necessary to remove the air bubbles in the specimens in order to ensure a stable interface among carbon bers and epoxy resins. The specimens of hybrids were fabricated with a lay-up process. During the impregnation with epoxy resins, both ends of the specimens were left non-impregnated to install electrodes. The impregnated carbon bers were cured at a temperature of 45 C for two days. The higher the temperature, the shorter the curing time is. However, if the curing temperature is higher than 50 C, the specimens tend to become curved. Electrodes were installed at the non-impregnated ends of carbon bers with silver paste and copper cables after the curing. Both cut ends were fully lled with conductive resins to improve the electrical contact with all carbon bers in the cross-section. The installation of electrodes is an important process for the fabrication of specimens. Any loose contact in the electrodes may lead to the instability of the electrical behaviors of the specimens. In order to ensure a good electrical contact between carbon bers and electrodes, the non-impregnated ends of carbon bers and copper cables were not only fully impregnated with conductive resins but also bonded together rmly with copper wires. Finally, the electrodes were coated with a layer of polymer for an insulating and protecting purpose after the electrodes were cured at 45 C for one or two days. Seven types of specimens were fabricated to study the basic electrical properties of the CFRPs and HCFRPs, among which three types were

3. Results and discussion 3.1. Electrical stability of the CFRPs and HCFRPs with time The long-term properties of sensors, including stability, durability, survivability, reliability, calibration and referencing, are important, especially for the sensors embedded in engineering structures. Since carbon bers are highly resistant against chemical corrosion, sensors made of them are inherently characterized by long-term durability. The fabrication as well as protection is an external factor that greatly inuences the life cycle of the CFRPs/HCFRPsbased sensors. In this study, the electrodes were bonded rmly with copper wires and coated with a layer of special polymer to improve the electrical stability and life cycle of the CFRPs and HCFRPs. In this sub-section, the electrical stability of dierent types of specimens was studied. Five types of specimens AC, F and G are taken as samples to address the ERtime behaviors of dierent types of CFRPs and HCFRPs. The initial ERs (R0) of these ve specimens are 11.250, 13.164, 5.388, 3.764 and 3.188 X, respectively. During the experiment, the ambient temperature was kept at about 22 C and the change in temperature was approximately 0.3 C. Fig. 1 shows the relationships between ER and time for dierent types of specimens under dierent constant currents. For these specimens, there exists some undulation in the DR/R0time curves. The undulation is mainly due to the ambient changes in temperature, humidity, electromagnetic inuence and so on. It is shown that the stability of DR/R0time curves increases with increasing the values of applied currents. For example, the undulation of DR/R0 at 0.5 mA due to the ambient changes is 10 times larger than that at 5 mA. From all the measured voltage data, it was found that the absolute change in voltage

Table 2 Composition of the specimens Specimen Composition C1 A B C D E F G 1 1 1 1 1 1 1 1 1 1 1 1 C5 C8

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C.Q. Yang et al. / Carbon 45 (2007) 30273035

0.06 0.04 0.02

A (0.5mA) A (1.5mA) A (3.0mA) A (5.0mA)

0.15 0.1 0.05

B (0.5mA) B (1.5mA) B (3.0mA) B (5.0mA)

R/R0 (%)

R/R0 (%)
0 40 80 120 160 200

0 -0.05 -0.1 -0.15

0 40 80 120 160 200

-0.02 -0.04 -0.06

Time (min.)

Time (min.)

0.2 0.1

0.8 0.6

R/R0 (%)

R/R0 (%)

-0.1 -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 0 40 80 120 160 200 C (0.5mA) C (1.5mA) C (3.0mA) C (5.0mA)

0.4 0.2 0 -0.2 -0.4 -0.6 0 40 80 120

F (0.5mA) F (1.5mA) F (3.0mA) F (5.0mA)

160

200

Time (min.)

Time (min.)

0.4

0.2

R/R0 (%)

-0.2

-0.4

G (0.5mA) G (1.5mA) G (3.0mA) G (5.0mA)

-0.6

-0.8

40

80

120

160

200

Time (min.)

Fig. 1. Relationships between ER and time under dierent constant currents: (a) specimen A, (b) specimen B, (c) specimen C, (d) specimen F and (e) specimen G.

due to the ambient changes was about 0.004 mV for almost all the currents and slightly increased with increasing the value of currents. For a small current such as 0.5 mA, the measured voltage is certainly small. As a result, an equal change in voltage results in a large change in DR/ R0 for small currents. For the currents of 3 mA and 5 mA, the undulation of DR/R0 is generally smaller than 0.07%; while for the current of 0.5 mA, the values may be even larger than 0.69% for the HM carbon bers of C8, as shown in Fig. 1ce. From these results, it may be concluded that to obtain an accurate ER measurement the value of current

should be larger than 1.5 mA. That is the reason why a current of 5 mA is used during the study of DR/R0T behaviors in the following section. It is also demonstrated in Fig. 1 that the undulation of DR/R0 is largest for C8 and smallest for C1. For the HCFRPs containing C8, the undulation of DR/R0 is still relatively large in comparison with the undulations of C1 and C5. To improve the electrical stability and ER measurement accuracy of the HCFRPs containing C8, a higher current should be employed, or the volume content of C8 in the hybrids is controlled at a low level.

C.Q. Yang et al. / Carbon 45 (2007) 30273035

0.06 0.04 0.02 A (3mA) B (3mA) C (3mA) F (3mA) G (3mA) 140 120 100 A B C F G

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R/R0 (%)

0 -0.02 -0.04

Volt (mV)

80 60 40

-0.06 20 -0.08 -0.1 0 40 80 120 160 200 0 0 2 4 6 8 10 12

Time (min.)
0.12 0.1 0.08 0.06 A (5mA) B (5mA) C (5mA) F (5mA) G (5mA)

Current (mA)

Fig. 3. Currentvoltage characteristics of dierent types of specimens.

0.04 0.02 0

-0.02 -0.04 -0.06 -0.08 0 40 80 120 160

Time (min.)

Fig. 2. Comparison of DR/R0time stability of dierent types of specimens at constant currents: (a) 3 mA and (b) 5 mA.

The comparison of the DR/R0time stability of dierent specimens at currents of 3 mA and 5 mA is shown in Fig. 2a and b, respectively. It is shown that the ER is relatively stable with time, and the undulation of DR/R0 is smaller than 0.08%. Especially for specimens A, B and G, the variation in DR/R0 is even smaller than 0.03%, which demonstrates the good electrical stability of the CFRPs and HCFRPs. Under constant currents and temperature, the electrical stability is best for C1 and worst for C8. To improve the electrical stability and ER measurement accuracy of the CFRP and HCFRPs that consist of C8, a larger signal current should be applied. From Figs. 1 and 2, it is revealed that the stability of ER is related to the initial ER of the specimens. At the same measurement condition, the undulation of DR/R0 decreases with increasing the initial ERs. As elucidated above, the absolute change in voltage due to the ambient changes is about 0.004 mV for almost all the specimens, and therefore the undulation of DR/R0 is smaller for the specimens with a larger R0. To improve the electrical stability and ER measurement accuracy of the CFRPs and HCFRPs with a small initial ER, a large current should be employed, accordingly. 3.2. Voltampere behaviors of carbon bers and their hybrids The above section shows that the electrical stability and ER measurement accuracy of the specimens are related to

the type of carbon bers, values of current and their initial ERs. In this sub-section, the currentvoltage characteristic of dierent types of carbon tows is studied. Fig. 3 demonstrates the relationships between current and voltage for dierent types of specimens, where a graphitic type of conductivity is exhibited. The voltage increases with applied current linearly, which demonstrates a linear resistance characteristic for C1, C5, C8 and their hybrids. For the other types of specimens, the same linear currentvoltage characteristic is demonstrated. The results reveal that carbon bers and their hybrids are typical Ohmic and graphitic-type conductive materials. These mean that the ER of carbon bers and their hybrids is theoretically independent of the values of current. However, the currentvoltage characteristic of the CFRPs lled with short carbon bers and carbon blacks was related to the volume content of SCFs and CBs. A non-Ohmic behavior was exhibited when the volume content of SCFs was smaller than 8%; while, an Ohmic behavior was exhibited when the content was larger than 20% [18]. The comparison of currentvoltage characteristic reveals that the conductive mechanism of the CFRPs reinforced with CCFs is dierent from those lled with SCFs and CBs. The electrical conductivity of the CFRPs reinforced with CCFs is mainly based on the graphitic conductivity of carbon bers, and an Ohmic electrical behavior is demonstrated. However, the electrical conductivity of the CFRPs lled with SCFs and CBs strongly depends on the ller content of the electrically conductive elements. According to the percolation theory, an electrically conductive network can be formed only when the ller content is beyond a percolation threshold. The value of threshold depends on the properties of conductive llers and polymer matrix. The tunneling, dielectric breakdown and some other factors also have some important inuences on the electrical behavior of the CFRPs lled with SCFs and CBs. 3.3. Dependence of electrical behaviors on temperature Provided that the transverse electrical conduction is negligible, according to the parallel circuit theory, the ER of

R/R 0 (%)

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C.Q. Yang et al. / Carbon 45 (2007) 30273035

3.0

i1

i2

n1 Y i1

! Ri

i3

i1

mk1

R/R0 (%)

hybrid specimens containing n types of carbon bers is given as , n n n k 1 n Y Y Y Y Y Rhybrid Ri Ri R1 Ri Ri Rm 1

2.5

2.0

A (01) A (02) A (03)

1.5

1.0

where Ri is the ER of the ith type of carbon bers. The initial ERs of all the specimens are shown in Table 3. As expected, the hybrids are characterized by a smaller initial ER than those of their components of carbon bers. According to Eq. (1), the calculated ERs of specimens DG are 6.065, 3.643, 3.823 and 2.853 X, respectively. From the table, it is found that the experimental ERs of the hybrid specimens are a litter smaller than the theoretical ones. The dierence between the theoretical and experimental ERs of hybrids may be due to two main reasons. One reason is due to the dispersion in material properties and the defection during the fabrication of specimens. The other is due to the transverse electrical conduction among carbon bers. The theoretical ERs calculated from Eq. (1) are not taken into account of the inuence of transverse electrical conduction among carbon bers. Factually, there exists some transverse electrical conduction among carbon bers, which had been investigated and reported in our previous work [8]. The specimens were heated and cooled for three cycles to study the relationship between DR/R0 and temperature as well as the ER recoverability. The relationships between DR/R0 and temperature for dierent types of CFRPs (specimens AC) are shown in Fig. 4. In the following section, the nth heating cycle of specimen m is labeled as m(n). For example, A(02) means the second heating cycle of specimen A. It is shown in Fig. 4 that the DR/R0T curves can be modeled accurately by the linear equation below: yDR=R0 a xT b 2

0.5

0.0

10

20

30

40

50

60

70

T (C)
2.5

R/R0 (%)

1.5 B (01) 1 B (02) B (03) 0.5

10

20

30

40

50

60

70

T (C)
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0

R/R0 (%)

C (01) C (02) C (03)

10

20

30

40

50

60

70

where a and b are the slope and intercept of the tting curve. The tting curve of the second heating cycle of each type of specimen is listed in Table 3. In this table, R2 is correlation coecient of the DR/R0T curve, which describes the similarity between the DR/R0T curve and its tting line. It is demonstrated that the value of R2 of all tting lines is larger than 0.983. This indicates that the ER of carbon bers increases with temperature in a good linear manTable 3 Initial ERs, tting curves and NTCs of dierent types of specimens Specimen A Initial ER (X) a b R2 NTC 11.250 0.0372 0.024 0.9995 0.038 B 13.164 0.033 0.0000 0.9993 0.033 C 5.388 0.1069 1.1444 0.9839 0.094

T (C)

Fig. 4. Relationships between (DR/R0) and temperature for the CFRPs reinforced with single type of carbon bers: (a) specimen A, (b) specimen B and (c) specimen C.

ner. Among all the CFRPs, the linearity of the DR/R0T curve is best for the CFRP reinforced with C1 and worst

D 6.566 0.0292 0.0386 0.9983 0.029

E 3.922 0.0578 0.0479 0.9912 0.041

F 3.764 0.0881 0.1658 0.9962 0.089

G 3.188 0.0708 0.0845 0.9968 0.067

C.Q. Yang et al. / Carbon 45 (2007) 30273035

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for that reinforced with C8. The linearity of the DR/R0T curves increases with the decrease in the elastic modulus of carbon bers. The relationships between DR/R0 and temperature for the hybrid specimens DG are shown in Fig. 5. For these specimens, the ER decreases linearly with increasing the temperature as the specimens reinforced with single type of carbon bers. All the DR/R0T curves can be well tted with lines with a R2 not smaller than 0.9958. As revealed in Table 3, the hybridization with HS and MM carbon bers can improve the linearity of the CFRP reinforced with HM carbon bers. It is shown in Fig. 5 that for the specimens consisting of C8 the dispersion among dierent heating cycles becomes larger as the volume fraction of C8 increases. To obtain a good recoverability of DR/R0T behavior, the volume fraction of C8 should be controlled at a low level. Figs. 4 and 5 conrm that the relationships between DR/R0 and T are linear and reversible for all types of specimens. To quantitatively characterize the inuence of temperature on the electrical behavior of the CFRPs and HCFRPs, a parameter, termed negative temperature coecient (NTC), is dened as NTC DR=R0 =DT 3

The average NTCs of all specimens are listed in Table 3. The CFRP reinforced with HM carbon bers of C8 is characterized by a largest NTC, and that reinforced with MM carbon bers of C5 is characterized by a smallest NTC. It is also found that the dispersion among dierent heating cycles is larger for the CFRP reinforced with HM carbon bers than for those reinforced with HS and MM carbon bers. From Table 3, Figs. 4 and 5, it is indicated that for the specimens consisting of C8 the NTC becomes larger with increasing the volume fraction of C8. For all the specimens, a NTC electrical behavior is shown within a temperature range from 0 C to 70 C. A similar NTC behavior of the CFRP composites had been found and reported but without details [17,26,27]. Ogi [17] found the NTC behavior in 90 direction of the CFRPs but not in 0 and 45 directions. The dependence of ER on temperature was relatively complicated for the CFRPs lled with SCFs and CBs. It was reported that before the melting point of polymer matrix a PTC electrical behavior was demonstrated, and around the melting point a steep NTC behavior was demonstrated [1822]. The PTC behavior was believed due to the dierence in the thermal expansion coecients between the polymer matrix and SCFs/CBs llers. The dierent expansion, which took place before the melting point of polymer

2.5

4.5 4.0 E (01) 3.5 D (01) 3.0 E (02) E (03)

2.0

R/R0 (%)

1.5 D (02) 1.0 D (03)

R/R0 (%)
20 30 40 50 60 70

2.5 2.0 1.5 1.0 0.5

0.5

0.0 0 10

0.0 0 10 20 30 40 50 60 70

T (C)
6.5 6.0 5.5 5.0 4.0 3.5 G (02) G (03) 4.5 5.0 4.5 G (01)

T (C)

R/R0 (%)

R/R0 (%)
20 30 40 50 60 70

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0

F (01) F (02) F (03)

3.0 2.5 2.0 1.5 1.0 0.5

10

0.0 0 10 20 30 40 50 60 70

T (C)

T (C)

Fig. 5. Relationships between (DR/R0) and temperature for the HCFRPs reinforced with multi-types of carbon bers: (a) specimen D, (b) specimen E, (c) specimen F and (d) specimen G.

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C.Q. Yang et al. / Carbon 45 (2007) 30273035

matrix, resulted in the breakup of the electrically conductive networks with a consequent increase in resistivity [20]. The NTC behavior had been explained in terms of the formation of new networks of conductive elements and the reparation of disconnected conductive pathways [21,22]. The mechanism for the NTC behavior of the CFRPs reinforced with CCFs is dierent from that of the CFRPs lled with SCFs and CBs. It has been conrmed in the above section that the CFRPs/HCFRPs reinforced with CCFs are typical graphitic-type conductive materials, and the NTC is their inherent physical behavior. Due to these reasons, the DR/R0T behaviors of the CFRPs/HCFRPs reinforced with CCFs are relatively stable among dierent heating and cooling cycles, as is clearly demonstrated in Figs. 4 and 5. However, those of the CFRPs lled with SCFs or CBs were not so stable, and the ER at the same temperature increased as the heating and cooling cycles progressed. Since the DR/R0T behaviors are shown to be linear and reversible for all types of specimens, the as-researched CFRPs/HCFRPs reinforced with single or multi-types of carbon bers can be used as linear temperature sensors, temperature-switch and other applications. If used as temperature sensors, they are characterized by a long optional gauge-length and can provide a distributed temperature sensing through installing multi-electrodes. Moreover, they are very cheap and simple in comparison with other types of sensors. This investigation also reveals that if the CFRPs/HCFRPs are used as strain and/or damage sensors some countermeasures should be taken to compensate the inuence of temperature because the inuence of temperature on the electrical behaviors of the CFRPs and HCFRPs is unnegligible. In such cases, the temperature compensation may be performed through arranging a PTC resistor that is free from strain/stress along the CFRPs/HCFRPs in series within the same circuit. Another feasible method for temperature compensation is to add some electrically conductive llers in the polymer matrix to fabricate a PTC polymer matrix. Then a PTC resistor or polymer matrix can compensate the NTC behavior of the CFRPs and HCFRPs. The investigations on the temperature compensation for the CFRPs/HCFRPs are now under study. 4. Conclusions The values of current inuence the electrical stability and ER measurement accuracy of the CFRPs/HCFRPs. In general, the ER measurement accuracy increases with increasing the values of currents. To obtain an accurate ER measurement, the currents should be larger than 1.5 mA. It is also shown that the CFRPs/HCFRPs reinforced with CCFs are characterized by a typical Ohmic behavior and graphitic-type conductivity. Temperature has a great inuence on the electrical behaviors of the as-researched specimens. All the specimens studied in this paper show a NTC electrical behavior.

Among them, specimen C reinforced with HM carbon bers shows a largest NTC, and specimen B reinforced with MM carbon bers shows a smallest one. For the hybrid specimens that consist of HM carbon bers, the NTC increases with increasing the volume fraction of HM carbon bers. The DR/R0T curves of all specimens can be well tted by lines with a R2 larger than 0.9912. The relationships between DR/R0 and temperature are experimentally conrmed to be reversible and linear for all types of carbon bers. The results indicate that the CFRPs and HCFRPs studied in this study may be used as linear temperature sensors. References
[1] Abry JC, Choi YK, Chateauminois A, Dalloz B, Giraud G, Salvia M. In situ monitoring of damage in CFRP specimens by means of AC and DC measurements. Compos Sci Technol 2001;61:85564. [2] Shui XP, Chung DDD. A piezoresistive carbon lament polymer matrix composite strain sensors. Smart Mater Struct 1996;5:2436. [3] Wang SK, Chung DDD. Self-sensing of exural strain and damage in carbon ber polymermatrix composite by electrical resistance measurement. Carbon 2006;44:273951. [4] Ogi K, Takao Y. Characterization of piezoresistance behavior of a CFRP unidirectional laminate. Compos Sci Technol 2005;65:2319. [5] Park JM, Li SI, Choi JH. Cure monitoring and residual stress sensing of single carbon ber reinforced epoxy composites using electrical resistivity measurement. Compos Sci Technol 2005;65:57180. [6] Wu ZS, Yang CQ, Harada T, Ye LP. Self-diagnosis of structures strengthened with hybrid carbon-ber reinforced polymer sheets. Smart Mater Struct 2005;14:3951. [7] Yang CQ, Wu ZS. Theoretical/experimental investigations on electrical resistance change of carbon bers. In: Wu ZS, Abe M, editors. In: Proceedings of the rst structural health monitoring and intelligent infrastructure, Japan; 2003. p. 1295301. [8] Wu ZS, Yang CQ. Electrical and mechanical characterization of hybrid CFRP sheets. J Compos Mater 2006;40:22744. [9] Yang CQ, Wu ZS, Ye LP. Self-diagnosis of hybrid CFRP rods and as-strengthened concrete structures. J Intell Mater Syst Struct 2006;17(7):60918. [10] Schueler R, Joshi SP, Schulte K. Damage detection in CFRP by electrical conductivity mapping. Compos Sci Technol 2001;61:92130. [11] Li JR, Xu JR, Zhang MQ, Rong MZ. Carbon black/polystyrene composites as candidates for gas sensing materials. Carbon 2003;41: 235360. [12] Tsubokawa N, Tsuchida M, Chen J, Nakazawa Y. A novel contamination sensor in solution: the response of the electric resistance of a composite based on crystalline polymer grafted carbon black. Sens Actuators, B: Chem 2001;79:927. [13] Bakis CE, Nanni A, Terosky JA, Koehler SW. Self-monitoring, pseudo-ductile, hybrid FRP reinforcement rods for concrete applications. Compos Sci Technol 2001;61:81523. [14] Hayashi T. On the improvement of mechanical properties of composites by hybrid composites. In: Proceedings of the eighth international reinforced plastics concrete. Brighton, UK: British Plastics Federation; 1972. p. 14952. [15] Somboonsong W, Ko FK, Harris HG. Ductile hybrid ber reinforced plastic reinforcing bar for concrete structure: design methodology. ACI Mater J 1998;95:65566. [16] Muto N, Araki Y, Shin SG, Matsubara H, Yanagida H. Hybrid composites with self-diagnosing function for preventing fatal fracture. Compos Sci Technol 2001;61:87583. [17] Keiji O, Yoshihiro T. Electrical properties of carbon ber reinforced plastics and their application. J Jpn Soc Compos Mater 2002;28(6):22834.

C.Q. Yang et al. / Carbon 45 (2007) 30273035 [18] Chekanov Y, Ohnogi R, Asai S, Sumita M. Electrical properties of epoxy resin lled with short carbon bers. J Mater Sci 1999;34:558992. [19] Voet A. Temperature eect of electrical resistivity of carbon black lled polymer. Rubber Chem Technol 1981;54:4250. [20] Hindermann-Bischo M, Ehrburger-Dolle F. Electrical conductivity of carbon black-polyethylene composites: experimental evidence of the change of cluster connectivity in the PTC eect. Carbon 2001;39:37582. [21] Xi Y, Ishikawa I, Bin Y, Matsuo M. Positive temperature coecient eect of LMWPEUHMWPE blends lled with short carbon bers. Carbon 2004;42:1699706. [22] Zhang C, Ma CA, Wang P, Sumita M. Temperature dependence of electrical resistivity for carbon black lled ultra-high molecular

3035

[23] [24]

[25]

[26]

[27]

weight polyethylene composites prepared by hot compaction. Carbon 2005;43:254453. Kohler F. Resistance elements. US patent 3243753; 1966. Klason C, Kubat J. Anomalous behavior of electrical conductivity and thermal noise in carbon black-containing polymer at Tg and Tm. J Appl Polym Sci 1975;19:83145. Yi XS, Wu GZ, Ma DL. Property balance for polyethylene-based carbon black-lled conductive composites. J Appl Polym Sci 1998;67:1318. Schulte K, Baron Ch. Load and failure analysis of CFRP laminates by electrical resistivity measurements. Compos Sci Technol 1989;36:6376. Fukuda H. Processing of carbon ber reinforced plastics by means of Jouleheating. Adv Compos Mater 1994;3(3):15361.